The dimeric β-diketiminato calcium hydride, [(BDI)CaH]2 (BDI = HC{(Me)CN-2,6-iPr2C6H3}2), reacts with ZnMe2 to afford the bimetallic calcium zincate complex, [(BDI)Ca(μ-CH3)2Zn(μ-H)]2, which subsequently undergoes an intramolecular reaction to effect the formation of [(BDI)CaMe]2, a notable omission from the homologous series of β-diketiminato alkylcalcium derivatives.